The present invention relates to a process for the staining of wood, which comprises treating the unstained wood with an aqueous preparation comprising
a) at least one dye, and
b) at least one dye stabilizer of the formula (I) or (II)
in which
G1 and G2, independently of one another, are C1-C4alkyl or together are pentamethylene, Z1 and Z2 are methyl, or Z1 and Z2 form a bridging member which is unsubstituted or substituted by an ester, ether, hydroxyl, oxo, cyanohydrin, amido, amino, carboxyl or urethane radical,
E is oxyl or hydroxyl, and X is an inorganic or organic anion, and the total number of cations h corresponds to the total number of anions j, to a wood stain comprising a dye and a dye stabilizer of the formula (I) or (II), and to the use of this wood stain for the staining of wood.
|
5. An aqueous wood stain comprising at least one dye selected from the group consisting of the dyes of the formulae
and at least one dye stabilizer of the formula
in which E is oxyl or hydroxyl, R is hydrogen or methyl, and n is 1 or 2, if n is 1, R1 is hydrogen, C1-C18alkyl, C2-C18alkenyl, propargyl, glycidyl, C2-C50alkyl which is unsubstituted or substituted by one to ten hydroxyl groups and which may be interrupted by one to twenty oxygen atoms, or R1 is C1-C4alkyl substituted by carboxyl or --COOZ, in which Z is hydrogen, C1-C4alkyl or phenyl or in which Z is C1-C4alkyl substituted by --(COO-)nMn+, in which n is a number 1-3 and M is a metal ion from the first, second or third group of the Periodic Table or is Zn, Cu, Ni or Co, or M is a group nn+(R2)4, in which R2 is C1-C8alkyl or benzyl, if n is 2, R1 is C1-C12alkylene, C4-C12alkenylene, xylylene or C1-C50alkylene which is unsubstituted or substituted by one to ten hydroxyl groups and which may be interrupted by one to twenty oxygen atoms. 1. A process for the staining of wood, which comprises treating the unstained wood with an aqueous preparation comprising
at least one dye selected from the group consisting of the dyes of the formulae
and
b) at least one dye stabilizer of the formula
in which E is oxyl or hydroxyl, R is hydrogen or methyl, and n is 1 or 2, if n is 1, R1 is hydrogen, C1-C18alkyl, C2-C18alkenyl, propargyl, glycidyl, C2-C50alkyl which is unsubstituted or substituted by one to ten hydroxyl groups and which may be interrupted by one to twenty oxygen atoms, or R1 is C1-C4alkyl substituted by carboxyl or --COOZ, in which Z is hydrogen, C1-C4alkyl or phenyl or in which Z is C1-C4alkyl substituted by --(COO-)nMn+, in which n is a number 1-3 and M is a metal ion from the first, second or third group of the Periodic Table or is Zn, Cu, Ni or Co, or M is a group nn+(R2)4, in which R2 is C1-C8alkyl or benzyl, if n is 2, R1 is C1-C12alkylene, C4-C12alkenylene, xylylene or C1-C50alkylene which is unsubstituted or substituted by one to ten hydroxyl groups and which may be interrupted by one to twenty oxygen atoms. 3. A process for the staining of wood, which comprises firstly staining the unstained wood with an aqueous preparation comprising at last one dye selected from the group consisting of the dyes of the formulae
and then treating it with an aqueous preparation comprising a dye stabilizer of the formula
in which E is oxyl or hydroxyl, R is hydrogen or methyl, and n is 1 or 2, if n is 1, R1 is hydrogen, C1-C18alkyl, C2-C18alkenyl, propargyl, glycidyl, C2-C50alkyl which is unsubstituted or substituted by one to ten hydroxyl groups and which may be interrupted by one to twenty oxygen atoms, or R1 is C1-C4alkyl substituted by carboxyl or --COOZ, in which Z is hydrogen, C1-C4alkyl or phenyl or in which Z is C1-C4alkyl substituted by --(COO-)nMn+, in which n is a number 1-3 and M is a metal ion from the first, second or third group of the Periodic Table or is Zn, Cu, Ni or Co, or M is a group nn+(R2)4, in which R2 is C1-C8alkyl or benzyl, if n is 2, R1 is C1-C12alkylene, C4-C12alkenylene, xylylene or C1-C50alkylene which is unsubstituted or substituted by one to ten hydroxyl groups and which may be interrupted by one to twenty oxygen atoms. 2. A process according to
4. A process according to
6. An aqueous wood stain according to
|
|||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
The present invention relates to aqueous wood stains and to their use in a process for the staining of wood.
Stained woods, or the dyes applied to the wood often exhibit undesired bleaching or changes in shade as a result of the action of light and/or heat. Furthermore, the stained woods often display a colour unlevelness.
The use of solvent-containing wood stains for the photochemical and thermal stabilization of the (unstained) material wood is known, for example, from EP-A-0 943 665.
EP-A-0 479 075 discloses the treatment of wood with a wood stain comprising a colorant, a solvent and a stabilizer.
There continues to be a need for an improved protection of the stained wood against light and evolution of heat, and for a process which permits even penetration of the wood and uses low-solvent or solvent-free wood stains.
The object of the present invention was therefore to provide a process according to which the stained wood would satisfy today'requirements with regard to penetration, photostability and heat stability.
It has now been found that using the special wood stains described below it is possible to achieve good penetration and very good stabilization of stained wood.
Accordingly, the present invention provides a process for the staining of wood, which comprises treating the unstained wood with an aqueous preparation (stain) comprising
a) at least one dye and
b) at least one dye stabilizer of the formulae (I) or (II)
in which
G1 and G2, independently of one another, are C1-C4alkyl or together are pentamethylene,
Z1 and Z2 are methyl, or Z1 and Z2 form a bridging member which is unsubstituted or substituted by an ester, ether, hydroxyl, oxo, cyanohydrin, amido, amino, carboxyl or urethane radical,
E is oxyl or hydroxyl, and
X is an inorganic or organic anion, and
the total number of cations h corresponds to the total number of anions j.
Preference is given to dye stabilizers of the formulae (I) and (II) in which Z1 and Z2 are methyl or a bridging member containing 1-200 carbon atoms and 0-60 oxygen and/or nitrogen atoms.
X is, for example, phosphate, carbonate, bicarbonate, nitrate, chloride, bromide, bisulfite, sulfite, bisulfate, sulfate, borate, carboxylate, alkylsulfonate, arylsulfonate or phosphonate, for example diethylenetriaminepentamethylenephosphonate.
X as carboxylate is, in particular, a formate, acetate, benzoate, citrate, oxalate, tartrate, acrylate, polyacrylate, fumarate, maleate, itaconate, glycolate, gluconate, malate, mandalate, tiglate, ascorbate, polymethacrylate, nitrilotriacetate, hydroxyethylethylenediaminetriacetate, ethylenediaminetetraacetate or diethylenetriaminepentaacetate.
X is preferably chloride, bisulfite, bisulfate, sulfate, phosphate, nitrate, ascorbate, acetate, citrate, ethylenediaminetetraacetate or diethylenetriaminepentaacetate;
X is particularly preferably bisulfate or citrate.
h and j are preferably 1-5.
As a bridging member, Z1 and Z2 preferably contain 2 or 3 carbon atoms or 1 or 2 carbon atoms and a nitrogen or oxygen atom which together with the radical of the formulae (I) or (II) form a 5-membered or 6-membered heterocyclic ring which may be further substituted. The substituents of Z1 and Z2 can also contain radicals of sterically hindered amines. Preference is given to compounds of the formulae (I) and (II) containing 1-4, in particular 1 or 2, sterically hindered amines or sterically hindered ammonium radicals. Aryl is to be understood as meaning, for example, C6-C12aryl, in particular phenyl or naphthyl, especially phenyl.
The dye stabilizers given under b) can be used individually or as mixtures with one another.
Alkyl is to be understood as meaning, for example, C1-C18alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl.
Alkylene is to be understood as meaning, for example, methylene, 1,2-ethylene, 1,1-ethylene, 1,3-propylene, 1,2-propylene, 1,1-propylene, 2,2-propylene, 1,4-butylene, 1,3-butylen, 1,2-butylene, 1,1-butylene, 2,2-butylene, 2,3-butylene, or --C5H10--, --C6H12--, --C7H14--, --C8H16--, --C9H18--, --C10H20--, --C11H22--, --C12H24--, --C13H26--, --C14H28--, --C15H30--, --C16H32--, --C17H34-- and --C18H36--.
Cycloalkyl or cycloalkoxy are to be understood as meaning, for example, C5-C12-cycloalkyl or C5-C12-cycloalkoxy, such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl or cyclododecyl, cyclopentoxy, cycloheptoxy, cyclodecyloxy or cyclododecyloxy.
Cycloalkenyl is to be understood as meaning, for example, C5-C12cycloalkenyl, such as cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl or cyclononenyl.
Aralkyl and aralkoxy are preferably phenylalkyl or phenylalkoxyl, such as benzyl, benzyloxy, α-methylbenzyl, α-methylbenzyloxy, cumyl or cumyloxy.
Alkenyl radicals are, for example, C2-C18alkenyl, in particular allyl.
Alkynyl radicals are, for example, C2-C12alkynyl, in particular propargyl.
Acyl is, for example, a radical R(C═O)--, in which R is an aliphatic or aromatic radical.
Aliphatic or aromatic radical means, for example, an aliphatic or aromatic C1-C30hydrocarbon; for example aryl, alkyl, cycloalkyl, alkenyl, cycloalkenyl, bicycloalkyl, bicycloalkenyl, and a combination of these radicals.
Examples of acyl are C2-C12alkanoyl, C3-C12alkenoyl and benzoyl.
Examples of alkanoyl are formyl, propionyl, butyryl, pentanoyl, octanoyl and, in particular, acetyl.
Alkenoyl is preferably acryloyl or methacryloyl.
The alkyl substituents may be linear or branched.
Examples of C1-C6alkyl are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl and hexyl.
Examples of C2-C4alkenyl are ethenyl, propenyl and butenyl.
Examples of C1-C4alkyl which is interrupted by one or two oxygen atoms are --CH2--O--CH3, --CH2--CH2--O--CH3, --CH2--CH2--O--CH2--CH3, --CH2--O--CH2CH2--O--CH3 and --CH2--O--CH2--O--CH3.
Preference is given to the dye stabilizers given under b) chosen from the compounds A to EE and A* to EE* and III to IIIc
in which
E is oxyl or hydroxyl,
R is hydrogen or methyl,
in the formulae A and A*,
n is 1 or 2,
if n is 1,
R1 is hydrogen, C1-C18alkyl, C2-C18alkenyl, propargyl, glycidyl, C2-C50alkyl which is unsubstituted or substituted by one to ten hydroxyl groups and which may be interrupted by one to twenty oxygen atoms, or
R1 is C1-C4alkyl substituted by carboxyl or --COOZ, in which Z is hydrogen, C1-C4alkyl or phenyl or in which Z is C1-C4alkyl substituted by --(COO-)nMn+, in which n is a number 1-3 and M is a metal ion from the first, second or third group of the Periodic Table or is Zn, Cu, Ni or Co, or M is a group Nn+(R2)4, in which R2 is C1-C8alkyl or benzyl,
if n is 2,
R1 is C1-C12alkylene, C4-C12alkenylene, xylylene or C1-C50alkylene which is unsubstituted or substituted by one to ten hydroxyl groups and which may be interrupted by one to twenty oxygen atoms,
in the formulae B and B*,
m is 1 to 4,
if m is 1,
R2 is C1-C18alkyl, C3-C18alkyl interrupted by --COO--, C3-C18alkyl substituted by COOH or COO--, or R2 is --CH2(OCH2CH2)nOCH3, in which n is a number from 1 to 12, or R2 is C5-C12cycloalkyl, C6-C12aryl which is unsubstituted or is substituted by one to four C1-C4alkyl, or
R2 is --NHR3, in which R3 is C1-C18alkyl, C5-C12cycloalkyl, C6-C12aryl which is unsubstituted or is substituted by one to four C1-C4alkyl, or
R2 is --N(R3)2, in which R3 is C1-C18alkyl, C5-C12cycloalkyl, C6-C12aryl which is unsubstituted or is substituted by one to four C1-C4alkyl,
if m is 2,
R2 is C1-C12alkylene, C4-C12alkenylene, xylylene, C2-C12alkylene interrupted by --COO--, C3-C18alkylene substituted by COOH or COO--, or R2 is --CH2(OCH2CH2)nOCH2--, in which n is a number from 1 to 12, or
R2 is C5-C12cycloalkylene, C7-C15aralkylene or C6-C12arylene, or
R2 is --NHR4NH--, in which R4 is C2-C18alkylene, C5-C12cycloalkylene, C8-C15aralkylene or C6-C12arylene, or
R2 is --N(R3)R4N(R3)--, in which R3 and R4 are as defined above, or
R2 is --CO-- or --NH--CO--NH--,
if m is 3,
R2 is C3-C8alkanetriyl or benzenetriyl, or
if m is 4,
R2 is C5-C8alkanetetrayl or benzenetetrayl,
in the formulae C and C*,
R10 is hydrogen, C1-C18alkyl, C5-C12cycloalkyl, C7-C15aralkyl, C2-C18alkanoyl, C3-C5alkenoyl or benzoyl,
x is 1 or 2,
if x is 1,
R11 is hydrogen, C1-C18alkyl, C2-C18alkenyl, propargyl, glycidyl, C2-C50alkyl which is unsubstituted or substituted by one to ten hydroxyl groups and which may be interrupted by one to twenty oxygen atoms, or
R11 is C1-C4alkyl which is substituted by carboxyl or --COOZ, in which Z is hydrogen, C1-C4alkyl or phenyl, or in which Z is C1-C4alkyl which is substituted by --(COO-)nMn+, in which n is a number from 1-3, and M is a metal ion from the first, second or third group of the Periodic Table or is Zn, Cu, Ni or Co, or M is a group Nn+(R2)4, in which R2 is hydrogen, C1-C8alkyl or benzyl, or
if x is 2,
R11 is C1-C12alkylene, C4-C12alkenylene, xylylene, or C1-C50alkylene which is unsubstituted or is substituted by one to ten hydroxyl groups and which can be interrupted by one to twenty oxygen atoms,
in the formulae D and D*,
R10 has the meaning given above,
y is a number from 1 to 4, and
R12 has the meaning of R2,
In the formulae E and E*,
k is 1 or 2,
if k is 1,
R20 and R21, independently of one another, are C1-C12alkyl, C2-C12alkenyl or C7-C15aralkyl, or
R20 is hydrogen, or R20 and R21 are together C2-C8alkylene which can be substituted by hydroxyl, or C4-C22acyloxyalkylene or
if k is 2,
R20 and R21 are together (--CH2)2C(CH2--)2,
in the formulae F and F*,
R30 is hydrogen, C1-C18-alkyl, benzyl, glycidyl or C2-C6-alkoxyalkyl,
g is 1 or 2,
if g is 1,
R31 has the meaning of R1 if n is 1,
if g is 2,
R31 has the meaning of R1 if n is 2,
in the formulae G and G*,
Q1 is --NR41 or --O--,
E1 is C1-C3alkylene, or E1 is --CH2--CH(R42)--O--, in which R42 is hydrogen, methyl or phenyl, or
E1 is --(CH2)3--NH-- or E1 is a direct bond,
R40 is hydrogen or C1-C18alkyl,
R41 is hydrogen, C1-C18alkyl, C5-C12cycloalkyl, C7-C15aralkyl, C6-C10aryl, or R41 is --CH2--CH(R42)--OH, in which R42 is as defined above,
in the formulae H and H*,
p is 1 or 2,
T4 has the meaning of R11 if x is 1 or 2,
M and Y, independently of one another, are methylene or carbonyl, where M is, in particular, methylene and Y is carbonyl,
in the formulae I and I*,
these formulae are a repeating structural part of a polymer, in which T1 is ethylene or propylene, or a repeating structural part derived from a copolymer of an α-olefin and alkyl acrylate or methacrylate,
q is a number from 2 to 100,
Q1 is --N(R41)-- or --O--, in which R41 is as defined above,
in the formulae J and J*,
r is 1 or 2,
T7 has the meaning of R1 if n is 1 or 2 in the formula A,
in the formulae L and L*,
u is 1 or 2,
T13 has the meaning of R1 if n is 1 or 2 in the formula A, with the proviso that T13 is not hydrogen if u is 1,
in the formulae M and M*,
E1 and E2 are --CO-- or --N(E5)--, in which E5 is hydrogen, C1-C12alkyl or C4--C22alkoxy-carbonylalkyl, where E1 and E2 have different meanings,
E3 is hydrogen, C1-C30alkyl, phenyl which is unsubstituted or substituted by chlorine or C1-C4alkyl, naphthyl which is unsubstituted or substituted by chlorine or C1-C4alkyl, or C7-C12phenylalkyl which is unsubstituted or substituted by C1-C4alkyl,
E4 is hydrogen, C1-C30alkyl, phenyl, naphthyl or C7-C12phenylalkyl, or
E3 and E4 together form a C4-C17polymethylene which is unsubstituted or substituted by one to four C1-C4alkyl radicals, in particular by methyl,
in the formulae N and N*,
R1 has the meaning of R1 in the formula A if n is 1,
G3 is the direct bond, C1-C12alkylene, phenylene or --NH--G1--NH--, in which G1 is C1-C12alkylene,
in the formulae O and O*,
R10 has the meaning of R10 in the formula C,
in the formulae P and P*,
E6 is an aliphatic or aromatic tetravalent radical, in particular neopentanetetrayl or benzenetetrayl,
in the formulae T and T*,
R51 is hydrogen, C1-C18alkyl, C5-C12cycloalkyl or C6-C10aryl,
R52 is hydrogen or C1-C18alkyl, or
R51 and R52 together are C4-C8alkylene,
f is 1 or 2,
if f is 1,
R50 has the meaning of R11 in the formula C if x is 1, or R50 is --(CH2)zCOOR54, in which z is a number from 1 to 4 and R54 is hydrogen or C1-C18alkyl, or R54 is a metal ion from the first, second or third group of the Periodic Table or is --N(R55)4, in which R55 is hydrogen, C1-C12alkyl or benzyl,
if f is 2,
R50 has the meaning of R11 in the formula C if x is 2,
in the formulae U and U*,
R53, R54, R55 and R56, independently of one another, are C1-C4alkyl or together form pentamethylene,
in the formulae V and V*,
R57, R58, R59 and R60, independently of one another, are C1-C4alkyl or together form pentamethylene,
in the formulae W and W*,
R61, R62, R63 and R64, independently of one another, are C1-C4alkyl, or together form pentamethylene,
R65 is C1-C5alkyl,
M is hydrogen or oxygen,
in which, in the formulae X to CC and X* to CC*,
n is from 2 to 3,
G1 is hydrogen, methyl, ethyl, butyl or benzyl,
m is a number from 1 to 4,
x is a number from 1 to 4,
if x is 1,
R1 and R2, independently of one another, are C1-C18 alkyl which is unsubstituted or substituted by one to five hydroxyl groups and which may be interrupted by one to five oxygen atoms, or C5-C12cycloalkyl, C7-C15aralkyl, C6-C10aryl which is unsubstituted or substituted by one to three C1-C8alkyl, or R1 is hydrogen, or R1 and R2 together are tetramethyl, pentamethylene, hexamethylene or 3-oxapentamethylene,
if x is 2,
R1 is hydrogen, C1-C8alkyl which is unsubstituted or substituted by hydroxyl and may be interrupted by one or two oxygen atoms,
R2 is C2-C18alkylene which is unsubstituted or substituted by one to five hydroxyl groups and may be interrupted by one to five oxygen atoms, o-, m- or p-phenylene which is unsubstituted or substituted by one or two C1-C4alkyl, or R2 is --(CH2)kO[(CH2)kO]h(CH2)k--, in which k is a number from 2 to 4 and h is a number 1 to 40, or
R1 and R2 together with the two N atoms to which they are bonded form piperazine-1,4-diyl,
if x is 3,
R1 is hydrogen,
R2 is C4-C8alkylene interrupted by a nitrogen atom,
if x is 4,
R1 is hydrogen,
R2 is C6-C12alkylene interrupted by two nitrogen atoms,
R3 is hydrogen, C1-C8alkyl which is unsubstituted or substituted by hydroxyl and may be interrupted by one or two oxygen atoms,
p is 2 or 3, and
Q is an alkali metal salt, ammonium or N+(G1)4 in which G1 is as defined above
and in the formulae DD and DD*
m is 2 or 3,
if m is 2,
G is --(CH2CHR--O)rCH2CHR-- in which or is a number from 0 to 3, and R is hydrogen or methyl and
if m is 3,
G is glyceryl,
in the formulae EE and EE*
G2 or is --CN, --CONH2 or --COOG3, in which G3 is hydrogen, C1-C18alkyl or phenyl,
X is an inorganic or organic anion,
where the total amount of the cations h corresponds to the total amount of the anions j; and
in which, in the formulae III to IIIc,
A11 is OR101 or NR111R112,
R101 is C2-C4alkenyl, propargyl, glycidyl, C2-C6alkyl which is unsubstituted or substituted by one to three hydroxyl groups and may be interrupted by one or two oxygen atoms, or R101 is C1-C4alkyl which is substituted by carboxyl or an alkali metal, ammonium or C1-C4alkylammonium salts, or R101 is alkyl which is substituted by --COOE10, in which E10 is methyl or ethyl, R102 is C3-C5alkyl which is interrupted by --COO-- or by --CO--, or R102 is --CH2(OCH2CH2)cOCH3, in which c is a number from 1 to 4, or R102 is --NHR103, in which R103 is C1-C4alkyl,
a is a number from 2 to 4,
if a is 2,
T11 is --(CH2CHR100--O)dCH2CHR100--, in which d is 0 or 1, and R100 is hydrogen or methyl,
if a is 3,
T11 is glyceryl,
if a is 4,
T11 is neopentanetetrayl,
b is 2or 3,
if b is 2,
G11 is --(CH2CHR100--O)eCH2CHR100--, in which e is a number from 0 to 3 and R100 is hydrogen or methyl, and
if b is 3,
G11 is glyceryl,
R111 is hydrogen, C1-C4alkyl which is unsubstituted or substituted by one or two hydroxyl groups and may be interrupted by one or two oxygen atoms,
R112 is --CO--R113, in which R113 has the meaning of R111 or R113 is --NHR114, in which R114 is C1-C4alkyl which is unsubstituted or substituted by one or two hydroxyl groups and/or by C1-C2-alkoxy, or R111 and R112 together are --CO--CH2CH2--CO--, --CO--CH═CH--CO-- or --(CH2)6--CO--, with the proviso that if R113 is C1-C4alkyl, R111 is not hydrogen.
Important dye stabilizers for the process according to the invention are the compounds of the formulae A, A*, B, B*, C, C*, D, D*, Q, Q*, R, R*, S or S*, X, X*, Y, Y*, Z and Z*, in which E is oxyl or hydroxyl, and R is hydrogen,
in the formulae A and A*
n is 1 or 2,
if n is 1,
R1 is hydrogen, C1-C6alkyl, C2-C6alkenyl, propargyl, glycidyl, C2-C20alkyl which is unsubstituted or substituted by one to five hydroxyl groups and may be interrupted by one to ten oxygen atoms, or R1 is C1-C4alkyl which is substituted by carboxyl or --COOZ, in which Z is hydrogen or C1-C4alkyl,
if n is 2,
R1 is C1-C8alkylene, C4-C8alkenylene, C2-C20alkylene which is unsubstituted or substituted by one to five hydroxyl groups and may be interrupted by one to ten oxygen atoms,
in the formulae B and B*
m is 1 or 2,
if m is 1,
R2 is C1-C4alkyl, or R2 is CH2(OCH2CH2)nOCH3, in which n is a number from 1 to 12, or R2 is phenyl which is unsubstituted or substituted by one to three methyl groups, or R2 is --NHR3, in which R3 is C1-C4alkyl or phenyl which is unsubstituted or is substituted by one or two methyl groups,
if m is 2,
R is C1-C8alkylene, C4-C8alkenylene, or R2 is --CH2(OCH2CH2)nOCH2--, in which n is a number from 1 to 12,
R2 is NHR4NH, in which R4 is C2-C6alkyl, C8-C15aralkylene or C6-C12arylene, or R2 is --CO-- or --NHCONH,
in the formulae C and C*,
R10 is hydrogen or C1-C3alkanoyl,
x is 1 or 2,
if x is 1,
R11 is hydrogen, C1-C6alkyl or glycidyl, or R11 is C1-C4alkyl which is substituted by carboxyl or COOZ, in which Z is hydrogen or C1-C4alkyl,
if x is 2,
R11 is C1-C6alkylene,
in the formulae D and D*,
R10 is hydrogen,
y is 1 or 2, and
R12 has the meaning given above for R2,
in the formulae Y, Y*, Z and Z*,
x is 1 or 2,
if x is 1,
R1 and R2, independently of one another, are C1-C4alkyl, or R1 and R2 together form tetramethylene or pentamethylene,
R2 is hydrogen or C1-C4alkyl substituted by hydroxyl,
if x is 2,
R1 is hydrogen, or C1-C4alkyl substituted by hydroxyl,
R2 is C2-C6alkylene, and
R3 is as defined above.
Particularly important dye stabilizers for the process according to the invention are the compounds of the formulae A, A*, B, B*, C, C*, D, D*, Q, Q*, R and R*, in which E is oxyl or hydroxyl and R is hydrogen,
in the formulae A and A*,
h is 1,
R1 is hydrogen, C1-C4alkyl, glycidyl, C2-C4alkyl which is unsubstituted or substituted by one or two hydroxyl groups and may be interrupted by one or two oxygen atoms, or R1 is C1--4alkyl which is substituted by --COOZ, in which Z is hydrogen or C1-C4alkyl,
in the formulae B and B*,
m is 1 or 2,
R2 is C1-C4alkyl, or R2 is CH2(OCH2CH2)nOCH3, in which n is a number 1 to 4,
if m is 2,
R is C1-C8alkylene,
in the formulae C and C*,
R10 is hydrogen or C1-C2alkanoyl,
x is 1 or 2,
if x is 1,
R11 is hydrogen, C1-C4alkyl or glycidyl, or R11 is C1-C4alkyl which is substituted by --COOZ, in which Z is hydrogen or C1-C4alkyl,
if x is 2,
R11 is C1-C6alkylene,
in the formulae D and D*,
R10 is hydrogen,
y is 1 or 2, and
R12 has the meaning of R2.
Very particularly important dye stabilizers for the process according to the invention are the compounds:
(a) bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)sebacate;
(b) bis(1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate;
(c) 1-hydroxy-2,2,6,6-tetramethyl-4-acetoxypiperidinium citrate;
(d) 1-oxyl-2,2,6,6-tetramethyl-4-acetamidopiperidine;
(e) 1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidine;
(f) 1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium bisulfate;
(g) 1-oxyl-2,2,6,6-tetramethyl-4-oxopiperidine;
(h) 1-hydroxy-2,2,6,6-tetramethyl-4-oxopiperidine;
(i) 1-hydroxy-2,2,6,6-tetramethyl-4-oxopiperidinium acetate;
(j) 1-oxyl-2,2,6,6-tetramethyl-4-methoxypiperidine;
(k) 1-hydroxy-2,2,6,6-tetramethyl-4-methoxypiperidine;
(l) 1-hydroxy-2,2,6,6-tetramethyl-4-methoxypiperidinium acetate;
(m) 1-oxyl-2,2,6,6-tetramethyl-4-acetoxypiperidine;
(n) 1-hydroxy-2,2,6,6-tetramethyl-4-acetoxypiperidine;
(o) 1-oxyl-2,2,6,6-tetramethyl-4-propoxypiperidine;
(p) 1-hydroxy-2,2,6,6-tetramethyl-4-propoxy-piperidinium acetate;
(q) 1-hydroxy-2,2,6,6-tetramethyl-4-propoxypiperidine;
(r) 1-oxyl-2,2,6,6-tetramethyl-4-(2-hydroxy-4-oxapentoxy)piperidine;
(s) 1-hydroxy-2,2,6,6-tetramethyl-4-(2-hydroxy-4-oxapentoxy)piperidinium acetate;
(t) 1-oxyl-2,2,6,6-tetramethyl-4-hydroxypiperidine;
(u) 1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidine;
(v) 1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium chloride;
(w) 1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium acetate;
(x) 1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium bisulfate;
(y) 1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium citrate;
(z) bis(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)citrate;
(aa) tris(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)citrate;
(bb) tetra(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)ethylenediaminetetraacetate;
(cc) tetra(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium)ethylenediaminetetraacetate;
(dd) tetra(1-hydroxy-2,2,6,6-tetramethyl-4-oxopiperidinium)ethylenediaminetetraacetate;
(ee) penta(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)diethylenetriaminepentaacetate;
(ff) penta(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium)diethylenetriaminepentaacetate;
(gg) penta(1-hydroxy-2,2,6,6-tetramethyl-4-oxopiperidinium)diethylenetriaminepentaacetate;
(hh) tri(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)nitrilotriacetate;
(ii) tri(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium)nitrilotriacetate;
(jj) tri(1-hydroxy-2,2,6,6-tetramethyl-4-oxopiperidinium)nitrilotriacetate;
(kk) penta(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)diethylenetriaminepentamethylenephosphonate;
(ll) penta(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium)diethylenetriaminepentamethylenephosphonate;
(mm) penta(1-hydroxy-2,2,6,6-tetramethyl-4-oxopiperidinium)diethylenetriaminepentamethylenephosphonate.
Preferred dye stabilizers in the process according to the invention are the compounds 1-oxyl-2,2,6,6-tetramethyl-4-hydroxypiperidine; 1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidine; 1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium chloride; 1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium acetate; 1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium bisulfate; 1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium citrate; bis(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)citrate; tris(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)citrate; tetra(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)ethylenediaminetetraacetate; tetra(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium)ethylenediaminetetraacetate; tetra(1-hydroxy-2,2,6,6-tetramethyl-4-oxopiperidinium)ethylenediaminetetraacetate; penta(1-hydroxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium)diethylenetriaminepentaacetate; penta(1-hydroxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium)diethylenetriaminepentaacetate and penta(1-hydroxy-2,2,6,6-tetramethyl-4-oxopiperidinium)diethylenetriaminepentaacetate.
The dye stabilizer which is very particularly preferably used in the process according to the invention is the compound 1-oxyl-2,2,6,6-tetramethyl-4-hydroxypiperidine of the formula
The compounds given above and used as dye stabilizers, and the preparation thereof are known, for example, from EP-A-0 943 665.
The present invention further provides for the use of the dye stabilizers of the formulae
as compositions for protecting stained woods against the effect of light and heat, where G1, G2, Z1, Z2, E, X, h and j have the meanings and preferred meanings given above.
The dye stabilizers of the formula (I) or (II) are usually used in an amount of from 1 to 10% by weight, preferably 2 to 6% by weight, based on the weight of the wood to be treated.
Dyes which are suitable for use in the process according to the invention for the staining of wood are all customary dyes used in wood staining. In particular, acid dyes, and also cationic dyes, reactive dyes, and metal complex dyes are suitable for use in the process according to the invention.
Acid dyes are, for example, those dyes described in the Colour Index, 3rd edition (3rd revision 1987 including Additions and Amendments up to No. 85) under "Acid Dyes". The anionic dyes which can be used may belong to a wide variety of dye classes and may contain one or more sulfonic acid groups. Examples are triphenylmethane dyes with at least two sulfonic acid groups, heavy-metal-free monoazo and disazo dyes each with one or more sulfonic acid groups and heavy-metal-containing, namely copper-, chromium-, nickel- or cobalt-containing monoazo, bisazo, azomethine and formazan dyes, in particular metallized dyes which contain two molecules of azo dye or one molecule of azo dye and one molecule of azomethine dye bonded to a metal atom, especially those which contain mono- and/or disazo dyes and/or azomethine dyes as ligands, and a chromium or cobalt ion as central atom, and also anthraquinone dyes, in particular 1-amino-4-arylaminoanthraquinone-2-sulfonic acids and 1,4-diarylamino- or 1-cycloalkylamino-4-arylaminoanthraquinonesulfonic acids.
Examples of cationic dyes are those dyes which are described in the Colour Index, 3rd edition, (3rd revision 1987 including additions and amendments up to No.85) under "Basic Dyes". The cationic dyes which can be used may belong to a very wide variety of classes of dye. In particular, the cationic monoazo, anthraquinone and oxazine dyes are used in the process according to the invention.
Metal complex dyes are to be understood as meaning, for example, the metal-containing acid dyes described above under acid dyes, and also 1:1 or 1:2-metal complex dyes which do not have water-solubilizing groups, in particular do not have sulfo groups. Of the metal complex dyes, particular importance is given to the copper and cobalt complexes of azo, quinone oxime and hydroxyanthraquinone dyes.
The reactive dyes are, for example, those dyes described in the Colour Index, 3rd edition (3rd Revision 1987 including Additions and Amendments up to No.85) under "Reactive Dyes".
Examples of reactive dyes are dyes from the group of the monoazo, disazo, polyazo, metal complex azo, anthraquinone, phthalocyanine, formazan or dioxazine dyes which contain at least one reactive group. These dyes preferably also contain at least one sulfo group.
Reactive groups are understood as meaning radicals which are reactive towards fibres and which are able to react with the hydroxyl groups of cellulose, the amino, carboxyl, hydroxyl and mercapto groups of wool or silk, or with the amino or, where appropriate, the carboxyl groups of synthetic polyamides to form chemical covalent bonds. The reactive groups are usually joined to the dye radical directly or via a bridging element. Suitable reactive groups are, for example, those which have at least one substituent which can be detached from an aliphatic, aromatic or heterocyclic radical, or those in which the radicals have a radical suitable for reaction with the fibre material, for example a halogenotriazinyl, halogenopyrimidinyl or vinyl radical.
Of particular preference in the process according to the invention are the dyes of the formulae
The dyes of the formulae (1) to (53) are known.
Very particular preference is given in the process according to the invention to the dyes of the formulae (1), (2), (3), (8), (12), (26), (27), (28), (29), (30), (31), (34), (42), (46), (48), (49), (50), (51), (52) and (53).
The present invention further provides an aqueous wood stain comprising at least one dye suitable for the staining of wood and at least one dye stabilizer of the formulae (I) or (II)
where for G1, G2, Z1, Z2, E, X, h and j, and for the dyes used, the meanings and preferred meanings given above apply.
The wood stain according to the invention can also comprise further additives, for example UV absorbers, fungicides or insecticides. Examples of UV absorbers are the UV absorbers of the benzotriazole, 2-hydroxybenzophenone, 2-hydroxy-1,3,5-triazine and oxalanilide series. Examples of fungicides are 1-chloronaphthalene and pentachlorophenol. Examples of insecticides are DDT, cypermethrin, propiconazole and parathion.
Furthermore, the wood stain can comprise organic solvents, in particular glycols, polyglycols, ketones or glycol ethers, and especially alcohols.
Wood which can be stained and treated with the dye stabilizer used according to the invention is primarily to be understood as meaning shaped wooden bodies with extensive surfaces, for example wooden planks, plywood and chipboard, which may be veneered, carved wooden objects, and wooden sections glued, nailed or screwed together to give, for example, furniture, but also wood in finely divided form, for example wood chips or sawdust. Also suitable for the process according to the invention are thin wooden boards which are prepared by continuously shaving tree-trunks and which are joined together, e.g. glued together, only after they have been stained to give thicker boards or workpieces.
The treatment of the wood to be stained can be carried out, for example, by firstly staining the wood with a dye, optionally drying it and then treating it with a dye stabilizer of the formula (I) or (II), or by treating the wood to be stained directly with a wood stain comprising a dye and a dye stabilizer of the formula (I) or (II). The treatment of the stained wood with the dye stabilizer of the formula (I) or (II) can be carried out, for example, by treating the stained and optionally dried wood with an aqueous formulation of the dye stabilizer of the formula (I) or (II), or by incorporating the dye stabilizer of the formula (I) or (II) into a commercially available nitrocellulose lacquer with which the stained and optionally dried wood is then coated.
Depending on the nature and the type of wood, and the contact times of the wood stains comprising a dye stabilizer or a dye stabilizer and a dye, the dye can lie directly on the surface of the wood material or, advantageously, can penetrate deeper inside the wood.
The wood stain according to the invention is applied to the wood using customary methods, for example by immersing the wood in a bath of the wood stain, by paint-brushing, spraying or by knife-coating. The exposure time here can be up to several hours, and the temperature of the wood stain bath can generally be between 20 and about 110°C C. When the treatment is complete, the wooden objects are generally dried in the air at room temperature. The treated wood can, however, also be dried at elevated temperatures up to about 100°C C., e.g. in a convection drying cabinet.
The wood stain according to the invention can be used to treat all customary types of wood, for example pine, spruce, fir, oak, ash, beech, maple, walnut tree, pear tree, teak, mahogany, chestnut, birch tree, larch, hazelnut, lime tree, willow, poplar, elm, Scots pine, plane tree, obeche or aspen.
The examples below serve to illustrate the invention. Unless stated otherwise, the parts are parts by weight and the percentages are percentages by weight. The temperatures are given in degrees Celsius. The relationship between parts by weight and parts by volume is the same as that between grams and cubic centimetres.
A 100 ml bomb of a pressure dyeing apparatus is charged with a liquor consisting of 80 ml of water (adjusted to a pH between 6.5 and 7.0) and 0.08 g of the dye of the formula
To this are added 4.0 g of a 0.8 mm-thick obeche board.
The bomb is sealed and heated to 110°C C. After agitation for 4 hours at this temperature, the contents of the bomb are cooled, and the stained piece of wood is washed in cold water and dried.
An aqueous solution of 20.0 g/l of the dye stabilizer of the formula
is applied to the stained and dried piece of wood using a knife-coater (groove depth 24 microns) and dried.
This gives an even red coloration with complete penetration in the cross section and a very good light-fastness.
A 0.8 mm wooden board made of ash is sanded on the upper side using fine sandpaper, moistened with a cloth, dried and again very carefully sanded. All of the wood dust is then brushed off the surface.
Using a paintbrush or a hand coater, a stain consisting of
93 parts by weight of water,
4 parts by weight of the dye stabilizer of the formula (IIId) dissolved in the water and
3 parts by weight of a 20% aqueous commercial form of the dye of the formula
is applied to the wood surface prepared in this way in an amount of about 100 g/m2.
The stained wood is then dried in the air.
This gives a brilliant red-coloured wood with a very good light-fastness.
(The ready-stained wood can then be coated with a commercially available nitrocellulose lacquer.)
A 0.8 mm wooden board made of ash is sanded on the upper side using fine sandpaper, moistened with a cloth, dried and again very carefully sanded. All of the wood dust is then brushed off the surface.
Using a paint brush or hand coater, a dye preparation consisting of
97 parts by weight of water and
3 parts by weight of a 20% commercial form of the dye of the formula (45) is applied to the wood surface prepared in this way in an amount of about 100 g/m2 and dried.
The stained wood is then treated with a mordant consisting of
96 parts by weight of water and
4 parts by weight of the dye stabilizer of the formula (IIId).
The wood is then dried in the air.
This gives a brilliant red-coloured wood with a very good light-fastness.
(The ready-stained wood can then be coated with a commercially available nitrocellulose lacquer.)
A 0.8 mm wood board made of ash is sanded on the upper side using fine sandpaper, moistened with a cloth, dried and again sanded very carefully. All of the wood dust is then brushed off the surface.
Using a paint brush or hand coater, a dye preparation consisting of
97 parts by weight of water and
3 parts by weight of a 20% commercial form of the dye of the formula (45) is applied to the wood surface prepared in this way in an amount of about 100 g/m2 and dried.
The stained wood is then coated with a commercially available nitrocellulose lacquer in which
4 parts by weight of the dye stabilizer of the formula
has been incorporated into 96 parts by weight of the lacquer. The wood is then dried in the air.
This gives a brilliant red-coloured wood with a very good light-fastness.
The procedure is as stated in Examples 2 to 4, but using, instead of the dye of the formula (45), the same amount of the dye of the formula
This gives a blue-coloured wood with a very good light-fastness.
A 0.8 mm wooden board made of ash is sanded on the upper side using fine sandpaper, moistened with a cloth, dried and sanded again very carefully. All of the wood dust is then brushed off the surface.
Using a paint brush or hand coater, a stain consisting of
96 parts by weight of water,
3 parts by weight of the dye stabilizer of the formula (IIId) dissolved in the water and
1 part by weight of a 20% aqueous commercial form of the dye of the formula
is applied to the wood surface prepared in this way in an amount of about 100 g/m2.
The stained wood is dried in the air.
This gives a yellow-coloured wood with a very good light-fastness.
(The ready-stained wood can then be coated with a commercially available nitrocellulose lacquer.)
The procedure is as stated in Example 6, but using, instead of the dye of the formula (I), the same amount of the dye of the formula (2).
This gives a red-coloured wood with a very good light-fastness.
(The ready-stained wood can then be coated with a commercially available nitrocellulose lacquer.)
The procedure is as given in Example 6, but using, instead of the dye of the formula (1), the same amount of the dye of the formula (3).
This gives a blue-coloured wood with a very good light-fastness.
(The ready-stained wood can then be coated with a commercially available nitrocellulose lacquer.)
The procedure is as given in Example 6, but using, instead of the dye of the formula (1), the same amount of the dye of the formula (8).
This gives a blue-coloured wood with a very good light-fastness.
(The ready-stained wood can then be coated with a commercially available nitrocellulose lacquer.)
The procedure is as given in Example 6, but using, instead of the dye of the formula (1), the same amount of the dye of the formula (12).
This gives a blue-coloured wood with a very good light-fastness.
(The ready-stained wood can then be coated with a commercially available nitrocellulose lacquer.)
The procedure is as given in Example 6, but using, instead of the dye of the formula (1), the same amount of the dye of the formula (26).
This gives a yellow-coloured wood with a very good light-fastness.
(The ready-stained wood can then be coated with a commercially available nitrocellulose lacquer.)
The procedure is as given in Example 6, but using, instead of the dye of the formula (1), the same amount of the dye of the formula (27).
This gives a red-coloured wood with a very good light-fastness.
(The ready-stained wood can then be coated with a commercially available nitrocellulose lacquer.)
The procedure is as given in Example 6, but using, instead of the dye of the formula (1), the same amount of the dye of the formula (28).
This gives a brown-coloured wood with a very good light-fastness.
(The ready-stained wood can then be coated with a commercially available nitrocellulose lacquer.)
The procedure is as given in Example 6, but using, instead of the dye of the formula (1), the same amount of the dye of the formula (29).
This gives a Bordeaux red-coloured wood with a very good light-fastness.
(The ready-stained wood can then be coated with a commercially available nitrocellulose lacquer.)
The procedure is as given in Example 6, but using, instead of the dye of the formula (1), the same amount of the dye of the formula (30).
This gives an orange-coloured wood with a very good light-fastness.
(The ready-stained wood can then be coated with a commercially available nitrocellulose lacquer.)
The procedure is as given in Example 6, but using, instead of the dye of the formula (1), the same amount of the dye of the formula (31).
This gives a red-coloured wood with a very good light-fastness.
(The ready-stained wood can then be coated with a commercially available nitrocellulose lacquer.)
The procedure is as given in Example 6, but using, instead of the dye of the formula (1), the same amount of the dye of the formula (34).
This gives a black-coloured wood with a very good light-fastness.
(The ready-stained wood can then be coated with a commercially available nitrocellulose lacquer.)
The procedure is as given in Example 6, but using, instead of the dye of the formula (1), the same amount of the dye of the formula (42).
This gives a yellow-coloured wood with a very good light-fastness.
(The ready-stained wood can then be coated with a commercially available nitrocellulose lacquer.)
The procedure is as given in Example 6, but using, instead of the dye of the formula (1), the same amount of the dye of the formula (46).
This gives a black-coloured wood with a very good light-fastness.
(The ready-stained wood can then be coated with a commercially available nitrocellulose lacquer.)
The procedure is as given in Example 6, but using, instead of the dye of the formula (1), the same amount of the dye of the formula (48).
This gives a blue-coloured wood with a very good light-fastness.
(The ready-stained wood can then be coated with a commercially available nitrocellulose lacquer.)
The procedure is as given in Example 6, but using, instead of the dye of the formula (1), the same amount of the dye of the formula (49).
This gives a red-coloured wood with a very good light-fastness.
(The ready-stained wood can then be coated with a commercially available nitrocellulose lacquer.)
The procedure is as given in Example 6, but using, instead of the dye of the formula (1), the same amount of the dye of the formula (50).
This gives a blue-coloured wood with a very good light-fastness.
(The ready-stained wood can then be coated with a commercially available nitrocellulose lacquer.)
The procedure is as given in Example 6, but using, instead of the dye of the formula (1), the same amount of the dye of the formula (51).
This gives a black-coloured wood with a very good light-fastness.
(The ready-stained wood can then be coated with a commercially available nitrocellulose lacquer.)
The procedure is as given in Example 6, but using, instead of the dye of the formula (1), the same amount of the dye of the formula (52).
This gives a blue-coloured wood with a very good light-fastness.
(The ready-stained wood can then be coated with a commercially available nitrocellulose lacquer.)
A 0.8 mm wooden board made of ash is sanded on the upper side using fine sandpaper, moistened with a cloth, dried and then sanded again very carefully. All of the wood dust is then brushed off the surface.
Using a paintbrush or hand coater, a stain consisting of
91 parts by weight of water,
3 parts by weight of the dye stabilizer of the formula (IIId) dissolved in the water
3 parts by weight of the UV absorber of the formula
and
3 parts by weight of a 20% aqueous commercial form of the dye of the formula
is applied to the wood surface prepared in this way in an amount of about100 g/m2.
The stained wood is then dried in the air.
This gives a brilliant blue-coloured wood with a very good light-fastness.
(The ready-stained wood can then be coated with a commercially available nitrocellulose lacquer.)
The procedure is as given in Example 26, but using, instead of the UV absorber of the formula (100), the same amount of the UV absorber of the formula
This gives a blue-coloured wood with a very good light-fastness.
(The ready-stained wood can then be coated with a commercially available nitrocellulose lacquer.)
Koller, Stefan, Scheibli, Peter
| Patent | Priority | Assignee | Title |
| 7678381, | Nov 03 2003 | Ciba Specialty Chemicals Corp | Stabilized body care products, household products, textiles and fabrics |
| Patent | Priority | Assignee | Title |
| 5171328, | Oct 04 1990 | BASF Aktiengesellschaft | Stabilizer-containing wood stains |
| 5746778, | Aug 02 1994 | A.W. Faber-Castell Unternehmensverwaltung GmbH & Co. | Wood stain containing a stabilizing agent |
| 5814107, | Jul 31 1996 | BASF Aktiengesellschaft | Photochemically stabilized polyamide compositions |
| 6254724, | Jul 23 1997 | Ciba Specialty Chemicals Corp | Inhibition of pulp and paper yellowing using nitroxides, hydroxylamines and other coadditives |
| EP943665, | |||
| GB2328210, | |||
| JP11170686, |
| Executed on | Assignor | Assignee | Conveyance | Frame | Reel | Doc |
| Apr 05 2001 | KOLLER, STEFAN | CIBA SPECIALTY CHEMICALSC CORP | ASSIGNMENT OF ASSIGNORS INTEREST SEE DOCUMENT FOR DETAILS | 012027 | /0633 | |
| Apr 05 2001 | SCHEIBLI, PETER | CIBA SPECIALTY CHEMICALSC CORP | ASSIGNMENT OF ASSIGNORS INTEREST SEE DOCUMENT FOR DETAILS | 012027 | /0633 | |
| May 07 2001 | Ciba Specialty Chemicals Corporation | (assignment on the face of the patent) | / |
| Date | Maintenance Fee Events |
| Mar 22 2007 | M1551: Payment of Maintenance Fee, 4th Year, Large Entity. |
| Mar 31 2011 | M1552: Payment of Maintenance Fee, 8th Year, Large Entity. |
| Apr 07 2015 | M1553: Payment of Maintenance Fee, 12th Year, Large Entity. |
| Date | Maintenance Schedule |
| Oct 07 2006 | 4 years fee payment window open |
| Apr 07 2007 | 6 months grace period start (w surcharge) |
| Oct 07 2007 | patent expiry (for year 4) |
| Oct 07 2009 | 2 years to revive unintentionally abandoned end. (for year 4) |
| Oct 07 2010 | 8 years fee payment window open |
| Apr 07 2011 | 6 months grace period start (w surcharge) |
| Oct 07 2011 | patent expiry (for year 8) |
| Oct 07 2013 | 2 years to revive unintentionally abandoned end. (for year 8) |
| Oct 07 2014 | 12 years fee payment window open |
| Apr 07 2015 | 6 months grace period start (w surcharge) |
| Oct 07 2015 | patent expiry (for year 12) |
| Oct 07 2017 | 2 years to revive unintentionally abandoned end. (for year 12) |